Biochar is considered as a promising adsorbent due to its unique porous structure, large surface area and lightweight nature. In this study, pomelo peel was used as raw material, and graphene oxide was introduced as a functional material. High-temperature carbonization was employed to achieve simultaneous carbonization of pomelo peel and thermal reduction of graphene oxide, resulting in the preparation of a porous sponge-like biochar with high hydrophobicity, thermal stability and photothermal conversion capability. This biochar was successfully applied to the efficient separation of various oil–water mixtures, demonstrating excellent cyclic adsorption stability. Furthermore, by harnessing its photothermal conversion effect, efficient absorption of viscous oil product was achieved. This study proposes a facile biochar preparation strategy that can expand its application in the field of oil spill emergency treatment and promote the utilization of agricultural waste.